Lubricating oils



- size materials whic Patented De.12,,1 944 I LUBRICATING oILs Lloyd L. Davis, Bert H. Lincoln, and Gordon D.

Byrkit, Ponca City, Okla., asslg'nors, by mesne assignments, to The Lubri-Zol Development Corporation, Cleveland, Ohio, a corporation of Delaware I No Drawing. ,Application August 3, 1940,

" Serial N0. 351,120

24 Claims.

Our invention relates to improved lubricating oils and more particularly to lubricating oils having exceptionally high viscosity indices. This is a continuation in part or our copending applications, Serial Nos. 230,660 Pat. No. 2,236,896 and 330,370 Pat. No. 2,236,897. I

Two general methods of obtaining high vis-'- cosity index oils have been described in the literature of the art namely, the production of synthetic or synthetically treated oils with high viscosity index and the addition of various materials to ordinary or low viscosity index oils to improve them. Our products are of the first type and are intended to be used directly as lubricati'ri'g oils.

In the prior art of synthesizing oils of lubricating properties, various processes have been employed as well as various starting materials. For example, lubricating oils have been prepared by the action of polymerizing reagents such as aluminum chloride, ferric chloride, phosphoric acid and phosphates, boron fluoride, and the like, on lower oleflns such as ethylene, propylene, butylenes, and higher oleflns such as hexene, dctene, and even cetene, CicHaz. Various mixed olefins have been polymerized such as cracked gases, cracked paraflln wax and the like;

Synthetic lubricating oils have been prepared by various condensation reactions. For example, the condensation of halogenated wax or other petroleum fractions with aromatic hydrocarbons.

or other aromatic-compounds such as naphtha;

lene, diphenyl ether and. the like.

The productsof our invention are more .cheaply and easily made than other synthetic lubricating oils. They have-higher viscosity indices than any previously reported. Furthermore, we utilize nonlubricating fractions of petroleum to-produce these high quality lubricating oils. Our products are, like the so-called white oils, extremely stable of ordinary lubricating oils. By our processes, we convert materials of low economic value into products ofgreatly enhanced value.

One object of our invention is to provide lubrie eating oils having extremely high viscosity in"- dices.

Another object of our invention is to utilize nonlubricant petroleum fractions to produce improved lubricatingoils.

A further object of our invention is to synthemay beused to improve the characteristics of o dinary lubricating oils.

A still further object of our invention is to convert materials of low economic value into 55 was separated by means ofcrystallization from,

. fi valuable products by a commercially feasible process.'

Qther objects of our invention will appear in the course-of the following description.

Briefly our invention consists in the production of mixed cyclic and alkyl ethers of the type RXR' in which R is a high molecular weight, aliphatic radical having at least 13 carbon atoms,

such as may be obtained, for'example, from par.-

aflln wax; Xis an atomof an element selected from the right hand side of group VI of the periodic table such as oxygen, sulphur, selenium or tellurium; and R is an organic radical containing a carbocyclic or heterocyclic nucleus which may or .may notbear various alkyl or other substituting groups. It is necessary to have at least 13, carbon atoms in the aliphatic-radical inorder to obtain as'products lubricating oils having viscosities of at least seconds Saybolt at degrees F.

While ordinary lubricating oils have viscosity indices from as low as 40 for naphthenic oils to 90. or 100-far Pennsylvania oils, the products of our invention have viscosity indices of not less 1 than 90.

The aliphatic radicals of our products may be derived from any source and may be of various degrees of purity, that is, freedom from other types of radicals.- For example, cetyl chloride is a suitable source of the cetyl radical; .We may utilize paraffin hydrocarbons of various petroleum fractions as sources of aliphatic radicals including hydrocarbons of the heavy ends of ordinary "phatic radicals of the type described is a rela-' '40 toward oxidation and sludging, which is not true gasoline, kerosene, gas oil, paraflin wax, and higher paraflin hydrocarbons from natural or synthetic sources. One preferred source of alitiveiy pure monochlor parafiin wax, dichlor paraffln wax or the like. 1 V

In the prior art, references are made to monochloro parafiin, dichloro parafiin,ftrichloro paraflin, and the like. It is usually considered-that the product of direct chlorination is the com-- pound represented by the total chlorine content and therefore the desired compound We have found'that these products of chlorination are very crude mixtures of the chlorinated hydrocarbons and containurichlorinated hydrocarbons and the mono-, di--, and polychloro derivatives. The whole mixture cannot be consideredthe desired compound. For.examp1e,-a so-called tri-. chloro paraflin wax containing 24 per. cent chlorine, which correspondsvery closely to the percentage of chlorine in the trichloro compound,

, wax and more highly chlorinated waxes.

dichlor and higher chlor wax is the desired prodacetone at low temperatures. The least soluble portion consisted of unchlorinated wax. The next least soluble portion consisted of a mixture of monochloro wax and unchlorinated wax. The percentage of unchlorinated wax in the original mixture, supposedly "trichloro parafiin wax, was

found to be 7.2 per cent. Thus, even a "trichloro paraffin as so-called in the prior art, because of the total chlorin content, was in fact a crude mixture containing as much as 7.2 per cent of unchlorinated wax and quantities of monoand dichloro waxes, as well as trichloro wax and more highly chlorinated waxes. Its use would not'give the same results as a trichloro paraffin free of higher and lower chlorinated parafiin, since the products will contain unhalogenated paraflin hydrocarbons and mixed derivatives.

Even though the appropriate amount of chlorine is introduced in the wax to form a monochloro wax, we have found that the crude chlo- -I rination mixture contains, in addition to small tmounts of chlorine and hydrogen chloride and the desired monochlor wax, also unchlorinated When uct, the crude chlorination mixture will contain in addition to chlorine and hydrogen, less highly chlorinated waxes.

In contrast to the use of such a mixture, we have found it possible, as fully described below, to obtain a relatively pure monochlor compound free from unchlorinated hydrocarbon and free from more highly chlorinated compound. We may thus prepare (1) monohalogenated hydrocarbons substantially free from unhaiogenated hydrocarbons and more highly halogenated hydrocarbons; (2) dihalogenated hydrocarbons substantially free from unhalogenated hydrocarbons and monohalogenated hydrocarbons, as well as from halogenated hydrocarbons containing more than two atoms of halogen per molecule; and'(3) trihalogenated hydrocarbons free from halogen ated hydrocarbons containing fewer or more than three halogen atoms per molecule and free from unhalogenated hydrocarbons. We refer in this specification to these materials as relatively pure monohalogen compounds, relatively pure dihalogen compounds, etc.

The chlorination of most petroleum hydrocarbons lowers their melting points and, up to a certain point, the greater the extent of chlorination; that is, the more chlorine atoms per molecule, the lower the melting point. The decrease in melting point is stepwise, and this permits us to separate the unchlorinated hydrocarbons from the monochloro hydrocarbons and the monochloro hydrocarbons from the dichloro and higher chlorinated hydrocarbons. We can, for example, separate the unchlorinated wax from the airblown mixture by filter pressing at such temperatures that all of the chlorinated waxes are largely liquids, while the unchlorinated waxes are largely solid. The temperature for the pressing operation will depend, of course, on the character of the wax used v initially and will vary considerably depending on Forexample, at a temperature of this factor. from 80 degrees F. to 90 degrees F. the monochloro product formed by the chlorination of wax having a'melting point of 120 degrees F. will be liquid, while the unchlorinated wax will be solid,

enabling a ready separation to be effected.

Qther methods of separation, as for example, sweating, selective solvent extraction at various temperatures, the use of diluents followed by chilling and settling or filtering, and the like,

may be employed for separating solid unchlorinated wax from chlorinated portions, and for separating the monochloro wax from the more highly chlorinated portions, and so on. In separating relatively pure monochlor, dichlor, etc., hydrocarbons from such sources as the heavy ends of gasoline, kerosene and the like, we preferably use chilling only as a method of separation since in solution extremely low temperatures are required. Solvents may be used here, of .caursev but it is more convenient to depend simply on differences in melting point. It will be obvious to those skilled in the art that in these cases it is not practicable to employ differences in boiling point since the halogen derivatives of the lower hydrocarbons will have the same boiling range as unhalogenated higher boiling hydrocarbons in the same fraction of starting material.

The unchlorinated wax separated from the crude chlorination mixture may be recycled to the chlorination step to obtain further quantities of chlorinated waxes. It does not represent refractory material, and the same proportions of chlorination products are obtained from it as from fresh wax.

The liquid chlorinated waxes after separation of unchlorinated hydrocarbons consist largely of monochloro and dichloro waxes when approximately 10 or 20 per cent chlorine respectively is introduced into a starting wax, of, say, from to degrees F. melting point, but some polychloro wax may be present. These monoand dichloro waxes may be separated from each other by crystallization from acetone, using a solventchlor wax ratio of from 1 to 1 to 20 to 1. In preparing the solution, an elevated temperature may be employed to insure that the chloro waxes are completely dissolved in the solvent. The solution is then chilled to a temperature of between minus 15 degrees F. and minus 20 degrees F. when a paraffin wax of 115 degrees to 130 degrees F. melting point is used for the initial chlorination. The monochloro waxes are precipitated out nearly quantitatively, while the dichloro and polychloro waxes will remain in solution. The precipitated monochloro waxes may be readily separated by settling, filtering, 0r centrifuging.

We have also used other crystallization solvents such as methyl-ethyl ketone, acetone, benzene, methylene chloride, various other halogenated solvents as well as liquid propane or butane. Mixtures of two or more solvents may be used. The use of a particular one or combination of these solvents requires the experimental determination of the properproportions and temperatures necessary to obtain the desired separation of the crude chlorination mixture into the various stages of chlorine contents. Halogenated solvents serve to aid in the precipitation of unchlorinated wax, while benzene and hydrocarbon solvents increase the solubility of the more highly chlorinated materials.

After removing the monochlor wax, the solution may be chilled to a lower temperature or concentrated by distillation or evaporation of the solvent or both to precipitate the dichlor waxes which may be then separated. A further separation of the remaining liquid may be accomplished by repetition of these processes. In this manner, the crude chlorination mixtures may be separated into unchlorinated wax, monochlor wax, dichlor wax and polychlor wax. We proved the homogenity of our monochlor wax, for example, by chilling until approximately half of the sample had solidified. Solid and liquid portions were asaacaa separated by a filtration and contained 12.1. and 11.4 per cent chlorine respectively. In the case of the wax which had the 120 degrees F. melting point, batches showed chlorine contents of 10.2,

. 10.3, and 10.5 per cent. These values are veryclose to the theoretical or 10.0 per cent, our relatively pure monochlor wax i substantially free from unchlorinated wax .and more highly chlorinated waxes. We may prepare according to our invention similarly pure diand polychlor waxes free from unchlorinated wa and more highly chlorinated waxes.

- -Our parailin hydrocarbons are preferably obtained from petroleum, though itis to be under stood that any source rich in'hydrocarbons oi the paraflin series maybe used as starting materials in practicing our invention. Our method is particularly applicable to the higher"'paraflin hydrocarbons such as represented by ordinary ual chlorine, and then pressed at 85 degrees F. The unchlorinated wax was reserved for further the final product with respect to homologues is determined by the purity of the starting hydrocarbon. It is understood, of course, that when a pure hydrocarbon is employed, a correspondin ly pure halide is obtained. I

Having selected the hydrocarbon in accordance with the desired final product, we chlorinate the hydrocarbon until approximately that amount of chlorine is absorbed which will produce the monochloro com-pound when that .is the desired product, or approximately that amount or chlorine which will produce the dichloro compound when that is the desired product, etc.

In the case of parailin hydrocarbons having from 18 to 24 carbon atoms per molecule. that .is, a material having a melting point of approximatei ly 120 degrees F., about 10 is. cent added chlorine will prdduce substantially the equivalent of the monochlor product. The amount of chlorine.- tion may vary between 9 percent and 12 per cent withoutbeingdisadvantageous. Thepercentageof chlorine .introduced into the hydrocarbon just described will be approximately 17 per cent when a dichloro product is desired. The amount of chlorine introduced will be less in the case ,0:

the high molecular weight, higher melting hydrocarbons, and more in the case of the lower molecular weight, lower melting hydrocarbons,

tent oichlorination as indicated above.

.tated. contains theoretically 10.0 per cent chlorine. The.

ation is in progress, in order to determine the ex- Samples may be removed from time to time, and the specific gravity of these be determined in order to iollow the chlorination process. If desired, chlorine analyses may be conducted on samples of the material being chlorinated. After sufflcient chlorine has been introduced, we blow the mixture with air or an inert gas, such as carbon dioxide, until the hydrogen chloride and tree chlorine, it any, are substantially removed. Whileit is not essential, the' chlorination mixture or the separated relatively pure halogenated hydrocarbons may be given a stabilizing treatment with dilute aqueous solutions of sodium sulfite, sodium bisulflte, sulturou acid, potassium permanganate, sodium hypochlorite, or the like. I As an example of the manufacture of a relatively pure chlorinated hydrocarbon, we describe here the manufacture of a relatively pure monochloro wax which contains approximately 26 carbon atoms per molecule. We started with 723.4 parts of a hydrocarbon wax having a melting point of 120 degrees F. The wax was chlorinated until 72.5 parts by weight oi. chlorine had been absorbed. The chlorinated wax was airblown to remove hydrochloric acid and uncombined residchlorination. The liquid portion wa then dissolved in-acetone, 350 parts of crude chloro wax being dissolved in 3,226 parts of acetone. The

solution was chilled to minus 18 degrees F. and 185 parts by weight of solid monochloro wax containing 10.3 per cent chlorine ,was precipi- Monochlor ,wax from this paraffin wax monochlor wax was normally liquid at room temperature.

Dichloro waxes and polychlor 'o waxes prepared according to our. method are suitable for use inv any 01' the applications described in the prior art,

where such dichloro waxes and polychloro waxes are required.- Since they contain no unchlorinated wax or lower chlorinated wax, they are particularly emcient in these applications and are a distinct improvement over the prior art which used crude chlorination mixtures of approximately the proper chlorine content but tor a given number of chlorine atoms per molecule. The chlorination may be accomplished in anysuitable manner. We preier' to heat the hy- I drocarbon-to a temperature at least that 01' its melting point and pass chlorine gas throush'the melting hydrocarbon.- Agitation increases the efliclency oi chlorine absorption butis'not essen-' tial. The chlorination reaction i exothermic and I 1 the heat of .reaction is ordinarily ample to main.

tain the mixture in the liquid state without the addition 01 other heat, Large quantities of hydrogen chloride. gas are evolved .which are conducicd from the reaction chamber, together with unreactedlfchlorine; j The material being chlorinated is constantly weighed while the chlorin- "which consisted of unchlorinated wax and more highly chlorinated wax. L

While chlorine has been referred to above almost exclusively, it is to be understood that any of the halogens are suitable to make halogen derivatives of the paraffin hydrocarbons accord in to our fluorine may suitably be used to obtainthe corresponding bromides, iodidesand fluorides. For

some purposes to which the halides are to be put, the bromine compounds-are much to be desired over the chlorine compounds, since they'are considerablyumore reactive, Where this is the case, we halogenate with'bromine, using a halogen carrier, such as halides of antimony, phosphorus, iron, various metals, and the like, and separate the brominated mixture into its com- Donents as described above in the case of the chlorine compounds. The iodine compounds of the paraflin hydrocarbons. may be prepared by direct iodination or by "an indirect method.

I the indirect method, theabovedescribed separation of mono'-, di-., and polyhalogen derivatives may be employed in any step of the process. Thus we may separate a relatively pure monoor dichloro paraflin and convert it to the correspondmethodn Thus bromine, iodine, and

halogenated mixture into a crude iodinated mixture and then separate into the various stages of halogenation. Fluorine may be introduced into paraflin hydrocarbons directly or indirectly by analogous methods. For most purposes, however, we prefer to use the chlorine compounds because of the cheapness and availabilit of chlorine above all the other halogens.

In preparing the lubricating oils of our invention, we use these relatively pure monoclor waxes or dichlor-waxes and treat them with metal derivatives of cyclic hydroxy compounds. We prefer to use the cheap sodium salts but other alkali, alkaline earth and heavy metal salts of the hydroxy compounds may be used. The cyclic hydroxy compounds may be monocyclic, bicyclic or polycyclic, such as phenol, cresols, xylenols, phenylethyl alcohol, naphthols, hydroxydiphenyls, di-

and triphenyl carbinols, phenyl cyclohexanol,

methyl cyclopentanol, thionaphthols, and the like. Even heterocyclic phenols such as 8-hydroxy quinoline may be used. It appears to be particular advantageous to have at least one alkyl group attached to the ring as in p-tert. -butylphenol, octadecylphenol, pentacosylphenol, amyl cyclohexanol, and the like. Other substituting groups may be present as in p-nitrophenol, p-hydroxybenzaldehyde, amyl salicylate, p-hydroxyacetophenone, o-hydroxybenzophenone, phenol sulfonic acid, its salts, esters and amides, vanillin, eugenol, thymol, mesitol, carvacrol, o-chlorophenol, tri-iodophenol, penta/chlorophenol, nitrochlorophenols, o-methylaminophenol, picramic acid, m-hydroxyazobenzene, thiophenol, selenocresol, resorcinol, hydroquinone monomethyl ether, o-chlorobenzyl alcohol, phenylethyl alcohol, cinammyl alcohol, and the like.

The reaction whereby our lubricating oils are produced proceeds at satisfactory rates at about 200 degrees C. with most of the ring hydroxy compounds and most of the halogenated aliphates, but temperatures between 100 degrees C. and 300 degrees C. may be used; provided the reaction is not too slow or provided the product is not converted to dark colored products of relatively low viscosity index.

It will be obvious that our relatively pure wax compound and keep the mixture agitated during the reaction. Usually the mixture is more dimcult toagitate at first than afterthe reaction has proceeded for a time.

We add water to the reaction mixture and wash out metal halide and excess metal derivative from our synthetic oil. Usually the oil needs only to be dried and this may beaccomplished in any suitable manner.

For example, we may use a vacuum dehydrator.

The following examples are given as illustrations and not as limitations:

Example 1 v U and metal'derivative must be substantially dry in order to carry out this reaction. We may use A mixture of 1,425 parts of o-chlorobenzyl alcohol, 230 parts of sodium, and 3,000 parts of toluene were refluxed together until the sodium had reacted. Our relatively pure monochlor wax (2,000 parts) was added, toluene was distilled ofi, and the mixture held at 160-180 degrees C. for four hours. The cooled mixture was washed with ing iodine compound, or we may convert the crude water several steamed.

times, with dilute acid, then Example 2 The condensation product of 1,300 parts oi sodium cresolate with 3,210 parts of our relatively pure dichlor wax gives another chlorine-bearing product of our invention.

It is to be understood that any or all of these gen compounds to manufacture lubricating oils having. extremely high viscosity indices. While we do not wish to claim the old processes, we do wish to claim all novelty inherent in our processes as broadly as the state of the art permits.

If desired, our product may advantageously be prepared in such a manner as to leave some residual halogen. This halogen will remain in the aliphatic part of the ether molecule. For example, we may condena'a one molecular proportion of a relatively pure dichlor wax with one or 1.5 molecular proportions of a metal phenolate or alcoholate. Or we may cause the condensation to proceed so as to remove halogen completely from the aliphatic part of the ether but use a halogen-bearing aromatic hydroxy compound such as p-chlorobenzyl alcohol, o-chlorphenol or the like. If desired, a halogen-free condensation product may be halogenated to obtain a halogen-bearing lubricating oil. Any of these halogen-bearing products have superior lubricating properties, particularly in film strength as compared to the halogen-free lubricating oil.

The present invention therefore contemplates the use as lubricants or as lubricating compound addition agents, the halogen, and more specifically chlorine-bearing, derivatives of the condensation products above identified, as well as those generically and specifically identified in our copending application Ser. No. 330,370. These halogen, or more specifically chlorine-bearing, derivatives may be prepared as indicated by permitting some of the original halogen to remain in the condensation product, or a halogen-free condensation product may be prepared and the same then halogenated to the desired degree of halogenation.

- The condensation products to be halogenated (whether they are halogen-free or contain some residual halogen) may be halogenated to any desired degree depending upon the particular use for which the lubricant is designed, and their degree of halogenation will largely determine the manner in which they are used. The oils of the present invention which contain only a slight amount of halogen, such as chlorine, may be used in their pure state, i. e., undiluted with other oil, and the more highly halogenated end products may advantageously be. employed as addition agents either with plain mineral lubricat- I lng oil or with the synthetic oils above identified,

which may or may not also contain some halogen.

is either a synthetic oil of: the character above defined, or a plain refined mineral lubricating oil, and when the resultant composition is desired for-use in lubrication of internal combustion engines and other working parts 01 automobilesand the like, generally very greatly improved and generally between 1 per cent and per cent.

Factors which determine the percentage within which these materials are employed as addition agents are the type of oil base to which they are added and the uses for which the composition is designed.

Other elements such as sulfur, nitrogen or phosphorus may be present in our lubricating' oil molecule. For the former purpose we may use substituted reagents in the condensation such as p-nitrophenol, 2-chlor-3 amino-pentacosane, l-mercapto-naphthyl disulfide, hydroxylphenyl diphenyl phosphate, o-hydroxyphenyl diamylphosphine and the-like. The finished lubricating product may be so made that it will contain from 0.2 to 20% by weight of one of the halogens, sulfur, nitrogen, phosphorus orcombi nations of two or more of these. Generally quantities ranging from only 0.2 to 5.0% of these elements .are contained in the lubricant. We may add from 05m 20% of other oxygen bearing organic com- Y G-endoethylene-Ai -tetrahydro phthaiate, tin octadecyl phthalate, and the like.

Our halogen-bearing others are particularly suited for use when diluted with hydrocarbon oils or hydrocarbon oils containing othertaddends. They improve the viscosity index of the oil to which they are added and the film strength as well. Examples of some of these blends are:

It will be seen that we have accomplished the purpose of our invention; namely, to utlize petroleum hydrocarbons of low economic value topro- 'duce high viscosity index lubricating oils of great economic value..

It will be understood thatcertain features and subcombinations are of utility and may be em ployedwithout reference to other featuresand subcombinations. This. is contemplated by and is within the-scopeof our claims. Itis further obvious that various changes may be made in details within the scope of our claims without departing from the spirit of ourinvention. It is, therefore, to be understood that our invention is not to be limited to the specific details shown 5 and described.

\ Having thus described our invention, we claim:

over 90, comprising principally a halogen-bearing ether of the type RXR' where R is a high molecula! weight aliphatic radical having at least 13 carbon atoms, R is an organic radical containing at least one cyclic nucleus,- and X is an "atom of an element selected from the right-hand side of group VI of the periodic table, said halogen 5 bearing ether having a viscosity of at least 50 Saybolt at 100 F. V

2. A lubricating oil having a viscosity index of over 90, comprising principally a halogen-bearing thioether of the type RSR' where R is a high molecular weight aliphatic radical having at least 13 carbon atoms and R is an organic radical containing at least one cyclic nucleus, said halogen bearing ether having a viscosity of at least 50 Saybolt at 100 F.

3. A lubricating oilhaving a viscosity index of over 90, comprising principally a halogen-bearing seleno-ether of the type RSeR' where R is a high molecular weight aliphatic radical having at least 13 carbon atoms and R is an. organic radical containing at least one cyclic nucleus, said halogen bearing ct-her having aviscosity of at least 50 seconds Saybolt at 100 F.

4. A lubricating oil having a viscosity index of over 90, comprising principally a halogen-bearing telluro-ether of the type RTeR' where R is a high molecular weight aliphatic radical having at least 13 carbon atoms and R is an organic radcal containing at least one cyclic nucleus, said halogen bearing ether having a viscosity ofat least i0 seconds Saybolt at 100 F.

5. A lubricating oil having a viscosity index of over 90, comprising principally a halogen-bearing mixed cyclic-aliphatic thio-ether with at least 13 carbon atoms-in the aliphatic radical, said halogen bearing ether having a viscosity of at least 50 seconds Saybolt at 100-F,

' 6. A process for the production of lubricat ng oils having viscosity'indices of over 90, and vis cosities of at'least 50 seconds Say-bolt at 100 F., comprising the steps of halogenating paraffin hydrocarbons whose monochloro derivatives melt lower than the hydrocarbons themselves, separating the mono-, di-, and polyhalogenated hydrocarbons from each other and from unhalogenated' hydrocarbons and separately replacing the halogen of each of the said relatively pure halogenated hydrocarbons by reacting the same with a metal derivative" of a halogen-bearing cyclic hydroxy I compound of the typeRXHdn which R is an organi v nucleus and X is an element'selected from the 7. .A process for the manufacture of lubricate ing oils having viscosity indices of over 90, and

viscosities or at least 50 seconds Saybolt at n,

comprising the steps of ,halogenating paraflin hydrocarbons whose monoc hloro derivativesmelt lower than the hydrocarbons themselves, separating the mono-, (11-, and polyhalogenated hydrocarbonsfrom "each other and from unhalothe halogen of each of the said relatively pure bearing metal thio-phenolate.

a. A process for the production of lubricat- 1. A lubricating oil having a viscosity index of radicalcontaining at, least one cyclic right-hand side of group VI of the periodic table.

genated hydrocarbons and separately replacin -viscosities of at least 50 seconds Saybolt at 100 F.,

comprising the steps of halogenating paraffin hydrocarbons whose monochloro derivatives melt lower than the hydrocarbons themselves, separating the mono-, di-, and polyhalogenated hydrocarbons from each other and from unhalogenated hydrocarbons and separately replacing the halogen of each of the said relatively pure halogenated hydrocarbons by means of a halogenbearing cyclic thioalcohol.

10. A lubricating oil having a viscosity index of over 90, comprising principally a halogen-bearing ether of the type RXR' where R is a high molecular weight aliphatic radical having at least 13 carbon atoms and R is an organic radical containing at least one aromatic nucleus and X i an element selected from the right-hand side of group VI of the periodic table, said halogen bearing ether having a viscosity of at least 50 seconds Saybolt at 100 F.

11. A lubricating oil having a viscosity index ofover 90, comprising principally a halogen-bearing ether of the type ROR' where R is a high molecular weight aliphatic radical having at least 13 carbon atoms and R is an organic radical containing at least one cyclic nucleus, said halogen bearing ether having a viscosity of at least 50 seconds Sayboltat 100 F.

2. A lubricating oil having a viscosity index'of over 90, comprising principally a halogen-bearing mixed cyclic-aliphatic ether with at least 13 carbon atoms in the aliphatic radical, said halogen bearing ether having a viscosity of at least 50 seconds Saybolt at 100 F.

13. A lubricating oil having a viscosity index of over 90, comprising principally a halogen-bearing, high molecular weight alkyl ether of a phenol in which the aliphatic'radical contains at least 13 carbon atoms, said halogen bearing ether having a viscosity of at least 50 seconds Saybolt at 100 F.

14. A lubricating oil having a viscosity index of over 90, comprising principally a halogen-bearing ether of the type ROR' where R is a hi h molecular weight aliphatic rad cal having at least 13 carbon atoms and R' is the radical of a cyclic hydroxy compound, said halogen bearing ether having a viscosity of at least 50 seconds Saybolt at 100 F.

15. A lubricating oil having a viscosity index of over 90, comprising principally a halogen-bearing alkyl ether of an aromatic hydroxy compound in which the aliphatic radical contains at least 13 carbon atoms, said halogen bearing ether having a viscosity of at least 50 seconds Saybolt at 100 F.

16. A lubricating oil having 'a viscosity index ov over 90, comprisin principally a halogenbearing alkyl ether of -a substituted aromatic hydroxy compound-in which the aliphatic radical contains at least 13 carbon atoms, said halogen bearing ether having a viscosity of at least 50 seconds Saybolt at 100 F.

17. A lubricating oil having a viscosity of over 90, comprising principally a halogen-bearing high molecular weight alkyl ether of a substituted phenol in which the aliphatic radical contains at least 13 carbon atoms, said halogen bearing ether having a viscosity of at least 50 seconds Saybolt at 100 F.

18. A process for the production of lubricating oils having viscosity indices of over 90, and viscosities of at least 50 seconds Saybold at 100 F., comprising the steps of halogenating paraflin hydrocarbons whose monochloro derivatives melt lower than the hydrocarbons themselves, separating the mono-, di-, and polyhalogenated hydrocarbons from each other and from unhalogenated hydrocarbons and separately replacing the halogen of each of the said relatively pure halogenated hydrocarbons by means of a metal derivative of a halogen-bearing cyclic hydroxy compound.

19. A process for the manufacture of lubricating oils having viscosity indices of over 90, and viscosities of at least 50 seconds Saybolt at 100 F.,

' comprising the steps of halogenating parafiin hydrocarbons whose monochloro derivatives melt lower than the hydrocarbons themselves, separating the mono-, di-, and polyhalogenated hydrocarbons from each other and from unhalogenated hydrocarbons and separately replacing the halogen of each'of the said relatively pure halogenated hydrocarbons by means of a halogenbearing metal phenolate. 20. A process for the production of lubricating oils having viscosity indices of over 90 and viscosities of at least 50 seconds Saybolt at 100 F., comprising the steps of halogenating paraffin hydrocarbons whose monochloro derivatives melt lower than the hydrocarbons themselves, separating the mono-, di-, and polyhalogenated hydrocarbons from each-other and from unhalogenated hydrocarbons and separately replacing the halogen of each of the said relatively pure halogenated hydrocarbons by means of a metal derivative of a halogen-bearing aromatic alcohol,

21. A process for the production of lubricating oils having viscosity indices of over 90 and viscosities of at least 50 seconds Saybolt at 100 F., comprising the steps of halogenating paraflin hydrocarbons .whose monochloro derivatives melt lower than the hydrocarbons themselves, separating the mono-, di-, and polyhalogenated hydrocarbons from each other and from unhalogenated hydrocarbons and separately replacing the halogen of each of the said relatively pure halogenated hydrocarbons by means or a halogen-bearing cyclic alcohol.

22. A lubricating oil having a viscosity index of over 90 comprising principally a halogen-bearing ether of the type ROR' where R is a high molecular weight aliphatic radical having at least 13 carbon atoms and'R' is an organic radical containing at least one aromatic nucleus, said halogen bearing ether having a viscosity of at least 50 seconds Saybolt at 100 F.

23. A lubricating composition comprising a major proportion of lubricating oil and from .25% to 20% of a halogen-bearing ether of the type RXR' where R is a high molecular weight aliphatic radical having at least 13 carbon atoms, R is an organic radical containing at least one cyclic nucleus, and X is an atom of an element selected from the right-hand side of group VI of the periodic table, said halogen-bearing ether having a viscosity of at least 50 seconds Saybolt at 100 F. and a viscosity index 0!. over 90.

. 24. A lubricating composition comprising a major proportion 01' lubricating oil and from 25% to 20% of a halogen-bearing thioether of the type RSR where R is a high molecular weight aliphatic radical having at least 13 carbon atoms and 

